Polymers of 3-butene esters, their preparation and use

ABSTRACT

The specification describes various polymers having monomer of formula (I): ##STR1## In formula (I), R1 and R2 are, independently, hydrogen, a C 1  -C 24  alkyl group, an aromatic or heteroaromatic group, a C 3  -C 8  cycloalkyl or C 2  -C 7  heterocycloalkyl group, or a --C(O)R3 group. Preferably R1 and R2 are both a a --C(O)R3 group where R3 which can the same of different is selected from the group consisting of a C 1  -C 24  alkyl group, an aromatic or heteroaromatic group, a C 3  -C 8  cycloalkyl or C 2  -C 7  heterocyclic group; or a --CH 2  --C(O)--R4 group in which R4 is a C 1  -C 6  alkyl group. At lease one of R1 and R2 is a --C(O)R3 group. The polymer may be a homopolymer or a copolymer containing other ethylenically unsaturated monomers. The polymer may be used in a variety of coating compositions such as inks, adhesives, paints and films. Unique monomers where both R1 and R2 are acetoacetyl groups and novel monomers where R2 is an acetoacetyl group are also described.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part application based onapplication Ser. No. 08/956,533 filed Oct. 23, 1997 which isspecifically incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to polymers resulting from polymerizingethylenically unsaturated esters derived from 3,4-epoxy-1-butene orepoxybutene. The polymers may be homopolymers or copolymers containingother ethylenically unsaturated monomers. The polymers of the inventionmay be used in a variety of coating compositions such as inks,adhesives, paints, and films.

2. Description of the Related Art

The ring opening chemistry of epoxides is well known. (Evans et al., J.Chem. Soc. 248 (1949)). Opening an epoxide ring with a nucleophile cancreate one hydroxyl moiety or, depending on reaction conditions, twohydroxyl moieties. The hydroxyl groups can undergo further reaction. Thehydroxyl groups can, for example, be converted to esters by reactionwith carboxylic acids. Hydroxyl groups can also be converted toacetoacetic esters (Clemens, R. J., Chemical Reviews, 86:241-318 (1986);Witzeman, J. S., U.S. Pat. No. 5,051,529 (1991)).

Reacting an epoxide group with an acid anhydride can yield adisubstituted ester derivative (U.S. Pat. No. 5,623,086). Reacting anepoxide with an alcohol results in the formation of a hydroxy ether andis well known in the literature. The remaining hydroxyl group may befurther derivatized using, for example, carboxylic acids or anhydridesto form esters using methods well known to those skilled in the art.

The ring opening reaction of 3,4-epoxy-1-butene or epoxybutene withhydroxide base yields an ethylenically unsaturated diol,3-butene-1,2-diol, having the following structure: ##STR2## The twohydroxyl moieties provide a possible means by which furtherfunctionality may be added to the polymer. For example, U.S. Pat. No.2,504,082 describes the synthesis of the propenyl ester of1-hydroxy-2-methoxy-3-butene. U.S. Pat. No. 4,916,255 describes thesynthesis of the methacrylate ester of 1-hydroxy-2-methoxy-3-butene.

However, the polymerization of ethylenically unsaturated esters such asallyl esters has proven difficult. Homopolymerization of allyl esterssuch as allyl acetate is sluggish and results in a low molecular weightpolymer. Allyl esters will also only copolymerize with a few selectedunsaturated monomers such as vinyl esters or maleic anhydride (C. E.Schildknecht, Allyl Compounds and Their Polymers, Wiley-Interscience,1973).

Similarly, only a few monomers are known that will copolymerizeeffectively with vinyl esters. For a number of applications,particularly coatings, poly(vinyl acetate) needs to be modified withother monomers to provide a lower glass transition temperature, T_(g).Vinyl esters such as vinyl neodecanoate have been shown to be useful inlowering the T_(g) of poly(vinyl acetate), but are expensive. Othervinyl esters that have also been shown useful in reducing the T_(g) ofpoly(vinyl acetate) include butyl acrylate and 2-ethyl hexyl acrylate.Copolymers of vinyl acetate and butyl acrylate are heterogeneous due tothe differences in reactivity (e.g., C. Pichot, M. F. Llauro, Q. T.Pham, J. Polym. Sci.: Polym. Chem. Ed, 19, 2619-2633 (1981)). However,monomers that will copolymerize well with vinyl esters such as vinylacetate and result in polymers with functional groups available forpost-polymerization are not known in the art.

Therefore, a need exists in the art for functionalized ethylenicallyunsaturated esters which may be used as monomers and undergo facilepolymerization. Moreover, the needed monomers should not only be able toform high molecular weight polymers but also be able to copolymerizewith a variety of other ethylenically unsaturated monomers. It wouldalso be desirable that such a functionalized ethylenically unsaturatedmonomer contain functionality capable of surviving polymerization andundergoing further post-polymerization reaction.

SUMMARY OF THE INVENTION

The invention provides a polymer formed by the polymerization of anethylenically unsaturated monomer and a monomer of formula (I): ##STR3##where R1 and R2 are both an ester group. The invention also providescoating compositions containing such polymers.

The invention further provides a method of making a polymer containing amonomer of formula (I). The method involves the polymerization, such asfree-radical polymerization, of a monomer of formula (I) with anethylenically unsaturated monomer.

The invention still further provides a enamine functional polymerresulting from the reaction of an amine and the polymerization productof a monomer of formula (1) and an ethylenically unsaturated monomer. Informula (I), at least one of R1 and R2 is an acetoacetyl group. Theinvention also provides a method of making the enamine functionalpolymers.

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the invention is a polymer resulting frompolymerization of a monomer of formula (I): ##STR4## and, optionally, anethylenically unsaturated monomer. Mixtures of these monomers togetheror with other ethylenically unsaturated monomers may be used to preparepolymers of the invention. Preferably, the polymerization is afree-radical polymerization.

In formula (I), R1 and R2 are, independently, hydrogen, a C₁ -C₂₄ alkylgroup, an aromatic or heteroaromatic group, a C₃ -C₈ cycloalkyl or C₂-C₇ heterocycloalkyl group, or a --C(O)R3 group. R3 is a C₁ -C₂₄ alkylgroup, an aromatic or heteroaromatic group, a C₃ -C₈ cycloalkyl or C₂-C₇ heterocyclic group, or a --CH₂ --C(O)--R4 group where R4 is a C₁ -C₆alkyl group. In the monomers of formula (I), at least one of R1 and R2is a --C(O)R3 group forming an ester. Preferably, when R1 and R2 areboth a --C(O)R3 group, R3 is a --CH₂ --C(O)--R4 where R4 is methylgroup, i.e. an acetoacetyl group. When R1 is a methyl group, preferably,R2 is either an acetyl group or an acetoacetyl group. In anotherpreferred embodiment, R1 and R2 are both a --C(O)R3 group where R3 canbe the same or different. Preferably for R1 and R2, R3 is the same andis an ethyl, propyl, or 3-heptyl group to form respectively,3-butene-1,2-dipropyl ester, 3-butene-1,2-dibutyl ester, and3-butene-1,2-di-2-ethylhexyl ester.

The alkyl group of R1, R2 and R3 may be a linear or branched alkylgroup. Preferably, the alkyl group is a C₁ -C₁₂ alkyl group. Morepreferably, the alkyl group is, for example, a methyl, ethyl, propyl,isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl or3-heptyl group. The alkyl group of R4 may also be a linear or branchedalkyl group. Preferably, R4 is a C₁ -C₄ alkyl group. More preferably, R4is, for example, a methyl, ethyl, or propyl group.

Preferred aromatic and heteroaromatic groups described here include, butare not limited to, phenyl, furanyl, pyrrolyl, isopyrrolyl, thienyl,napthyl, pyridinyl, pyranyl, and benzyl. Preferred cycloalkyl groupsdescribed here are C₃ -C₆ cycloalkyl groups. More preferably, thecycloalkyl group is, for example, a cyclopropyl, cyclopentyl, orcyclohexyl group. The heterocycloalkyl groups described here arepreferably C₂ -C₅ heterocycloalkyl groups. More preferably, theheterocycloalkyl groups is, for example, an oxiranyl, aziridinyl,imidazolidinyl, pyrazolidinyl, piperidinyl, piperazinyl, or morpholinylgroup.

In addition, an alkyl group, aromatic or heteroaromatic group, or acycloalkyl or heterocyclic group may be substituted with groups such as,but not limited to, nitro, bromo, chloro, fluoro, hydroxy, and alkoxygroups. An aromatic or heteroaromatic group or cycloalkyl or heterocyclemay also be substituted with a C₁ -C₄ alkyl group. Possible heteroatomsfor heteroaromatic groups include nitrogen, oxygen, and sulfur.

The ethylenically unsaturated monomer can be any monomer which containsat least one ethylenically unsaturated group allowing it to becopolymerized with monomers of formula (1). Such monomers include, forexample, allylic compounds, vinylic compounds, styrenic compounds,α,β-unsaturated compounds, alkenes, acrylic compounds and the like.Examples of suitable ethylenically unsaturated monomers include, but arenot limited to, vinyl acetate, vinyl pivalate, vinyl neodecanoate, vinylneononanoate, vinyl neoundecanoate, vinyl crotonate, vinyl 2-ethylhexanoate, vinyl propionate, 4-vinyl-1,3-dioxolan-2-one; ethylene, epoxybutene; vinyl chloride, vinyl methacrylate; allyl alcohol, allylchloride, allyl acetate, allyl methacrylate, di-allylmalonate; dimethylmaleate, diethyl maleate, di-n-butyl maleate, di-octyl maleate, maleicanhydride; 3-butene-1,2-diacetate, 3-butene-1,2-dipropionate,3-butene-1,2-dibutyrate, 3-butene-1,2-dibenzoate; dimethyl itaconate,itaconic anhydride; crotonic acid and its esters, for example, C₁ -C₁₈alkyl crotonates; acrylonitrile; acrylamide, methacrylamide, butylacrylamide, ethyl acrylamide; acrylic acid; methyl acrylate, ethylacrylate, ethylhexyl acrylate, propyl acrylate, butyl acrylate, isobutylacrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, laurylacrylate, octyl acrylate, iso-octyl acrylate; methacrylic acid; methylmethacrylate, ethyl methacrylate, ethylhexyl methacrylate, propylmethacrylate, butyl methacrylate, isobutyl methacrylate, hydroxy ethylmethacrylate, hydroxy propyl methacrylate, octyl methacrylate, glycidylmethacrylate, carbodiimide methacrylate, methoxybutenyl methacrylate,isobornyl methacrylate, hydroxybutenyl methacrylate, isopropenylmethacrylate, iso-octyl methacrylate, cylcoaliphaticepoxy methacrylate;ethylformamide; styrene and α-methyl styrene. Vinyl esters ofneononanoic acid, neodecanoic acid and neoundecanoic aicd are availablefrom Shell Chemicals and are known as VEOVA-9, VEOVA-10, and VEOVA-11,respectively ("Introduction to VEOVA Monomers," a Shell Chemicalspublication). Preferably the ethylenically unsaturated monomer is thevinyl ester, vinyl acetate.

Another embodiment of the invention is a method of making a polymer ofthe invention. The method involves polymerizing, preferably underfree-radical polymerization conditions, a monomer of formula (I) asdescribed above and, optionally, an ethylenically unsaturated monomer,also as described above. Free radical polymerization of monomer (I) isachieved under conditions known by those skilled in the art. Thepolymerization is conducted in the presence of a free radical generatinginitiator. The free radical polymerization process may be a bulk,solution, emulsion, or suspension process. Preferably, the free radicalpolymerization process is a semi-batch solution or emulsion process.

The free radical generating initiator may be any conventional freeradical polymerization initiator. Examples of suitable initiatorsinclude, but are not limited to, azo(bis isobutyronitrile), benzoylperoxide, di-t-butyl peroxide, t-butyl peroctoate, t-amyl-peroxy-2-ethylhexanoate, and the like. Quantitative conversion of monomer (I) to thecorresponding polymer can be improved by using a more active freeradical initiator, i.e. one with a shorter half-life, conducting thepolymerization at a higher temperature, or using a higher concentrationof initiator.

If a solvent is used to carry out the polymerization process, solventswhich can solubilize both monomer (I) and the resulting polymer arepreferred. Examples of suitable solvents include, but are not limitedto, xylene, toluene, methyl amyl ketone, ethyl ethoxy propionate,propylene glycol monomethyl ether, ethylene glycol butyl ether, and thelike. Preferably, the solvent is either a glycol ether or a glycol etherester.

Polymerization of a monomer of formula (I), optionally with anotherethylenically unsaturated monomer, occurs through the ethylenicallyunsaturated group of each monomer. The polymer of the invention maycontain at least one pendant functional moiety through which furtherchemistry can be conducted. The pendant functional moiety may be anymoiety which can undergo further reactions including, for example,reacting with crosslinkers to form thermoset materials. Preferably, thependant functional moiety is a hydroxyl group, an acetoacetoxy group, ora combination thereof.

A crosslinker used with a polymer of the invention may be any materialcapable of reacting with an active hydrogen containing resin and includethose well known in the art. Preferably, the resin is aurea-formaldehyde, a melamine-formaldehyde, or an isocyanate resin.

Polymers of the invention are generally thermoset polymers and can beused in a variety of coating compositions such as paints, architecturalcoatings, maintenance coatings, industrial coatings, automotivecoatings, textile coatings, inks, adhesives, and coatings for paper,wood, and plastics, and the like as described, for example, in U.S. Pat.No. 5,539,073 incorporated in its entirety herein by reference.Accordingly, the invention relates to such coating compositioncontaining a polymer of the invention. The coating composition may besolvent-based or water-based. The polymers of the invention may beincorporated in those coating compositions in the same manner as knownpolymers and used with the conventional components and or additives ofsuch compositions. The coating compositions may be clear or pigmented.

Upon formulation, a coating composition containing a polymer of theinvention may then be applied to a variety of surfaces, substrates, orarticles, e.g., paper, plastic, steel, aluminum, wood, gypsum board, orgalvanized sheeting (either primed or unprimed). The type of surface,substrate, or article to be coated generally determines the type ofcoating composition used. The coating composition may be applied usingmeans known in the art. For example, a coating composition may beapplied by spraying or by coating a substrate. In general, the coatingmay be dried by heating but preferably is allowed to air dry.Advantageously, a coating employing a polymer of the invention may bethermally or ambiently cured. As a further aspect, the present inventionrelates to a shaped or formed article which has been coated with acoating compositions of the invention.

A coating composition according to the invention may comprise a polymerof the invention, water, a solvent, a pigment (organic or inorganic)and/or other additives and fillers known in the art. For example, alatex paint composition of the invention may comprise a polymer of theinvention, water, a pigment and one or more additives or fillers used inlatex paints. Such additives or fillers include, but are not limited to,leveling, rheology, and flow control agents such as silicones,fluorocarbons, urethanes, or cellulosics; extenders; reactive coalescingaids such as those described in U.S. Pat. No. 5,349,026; flattingagents; pigment wetting and dispersing agents and surfactants;ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments;extenders; defoaming and antifoaming agents; anti-settling, anti-sag andbodying agents; anti-skinning agents; anti-flooding and anti-floatingagents; fungicides and mildewcides; corrosion inhibitors; thickeningagents; plasticizers; reactive plasticizers; curing agents; orcoalescing agents. Specific examples of such additives can be found inRaw Materials Index, published by the National Paint & CoatingsAssociation, 1500 Rhode Island Avenue, NW, Washington, D.C. 20005.

Preferably, a coating composition of the invention is a latex paintcomposition, the latex paint composition may be used for interior and/orexterior coatings. Preferably, a latex paint composition according tothe invention contains a copolymer of a monomer of formula (I) and anethylenically unsaturated monomer, each as described above. In apreferred embodiment, the monomer of formula (I) is3-butene-1,2-dipropyl ester (EpBDP), 3-butene-1,2-dibutyl ester(EpBDBu), or 3-butene-1,2-di-2-ethylhexyl ester (EpBD2EH) and theethylenically unsaturated monomer is vinyl acetate.

Another embodiment of the invention is a monomer of formula (I):##STR5## In formula (I), R1 is a C₁ -C₂₄ alkyl group or an aromatic orheteroaromatic group as defined above and R2 is a --C(O)R3 group whereR3 is a C₁ -C₂₄ alkyl group, an aromatic or heteroaromatic group, a C₃-C₈ cycloalkyl or C₂ -C₇ heterocyclic group; or a --CH₂ --C(O)--R4 groupwhere R4 is a C₁ -C₆ alkyl group, all as defined above. Preferably, bothR1 and R2 are a --C(O)--CH₂ --C(O)--R4 group where R4 is methyl group,i.e. both R1 and R2 are an acetoacetyl group. In another preferredembodiment, R1 is a methyl group and R2 is either an acetyl group or anacetoacetyl group. Examples of suitable monomers of formula (I) include,but are not limited to, 1-acetoxy-2-methoxy-3-butene,1-acetoacetoxy-2-methoxy-3-butene, 3-butene-1,2-dipropionate,1,2-diacetoxy-3-butene, 3-butene-1,2-diol monoacetate,3-butene-1,2-diacetate, and 1,2-bisacetoacetate-3-butene.

Another embodiment of the invention relates to derivatizing a polymer ofthe invention to form an enamine functional polymer. In an enaminefunctional polymer, the enamine functionality serves to stabilize theacetoacetoxy-groups and protect them from hydrolysis. Enamine-functionalpolymers have been described in Moszner et al., Polymer Bulletin 32,419-426 (1994); European patent Application No. 0 492 847 A2; U.S. Pat.No. 5,296,530; U.S. Pat. No. 5,484,849; U.S. Pat. No. 5,484,975; andU.S. Pat. No. 5,525,662. These documents are incorporated here byreference.

An enamine functional polymer according to the invention results fromthe reaction of an amine and an acetoacetoxy functionalized polymer. Theacetoacetoxy functionalized polymer is the polymerization product of amonomer of formula (I): ##STR6## and, optionally, an ethylenicallyunsaturated monomer. In formula (I), R1 and R2 are, independently,hydrogen, a C₁ -C₂₄ alkyl group, an aromatic or heteroaromatic group, aC₃ -C₈ cycloalkyl or C₂ -C₇ heterocycloalkyl group, or a --C(O)R3 group.In a preferred embodiment, both R1 and R2 are a --C(O)R3 group. R3 is aC₁ -C₂₄ alkyl group, an aromatic or heteroaromatic group, a C₃ -C₈cycloalkyl or C₂ -C₇ heterocyclic group, or a --CH₂ --C(O)--R4 groupwhere R4 is a C₁ -C₆ alkyl group. In the acetoacetoxy functionalpolymer, in the monomers of formula (I), at least one of R1 and R2 is anacetoacetyl group. The acetoacetoxy functionalized polymer has one ormore pendant acetoacetoxy moieties.

In a preferred embodiment, enamine functional polymers may be preparedby reacting an amine with an acetoacetoxy functionalized polymer asdescribed above. The reaction stoichiometry uses at least one molarequivalent of amino (NH) groups to acetoacetoxy groups. The amine may beany amine which upon reaction with the pendant acetoacetoxy moiety ormoieties of the acetoacetoxy functionalized polymer forms an enaminegroup. Suitable amines include, for example, ammonia, primary amines andsecondary amines. Preparation of enamines from acetoacetoxy groups aredescribed in U.S. Pat. Nos. 5,296,530, 5,484,975, and 5,525,662 whichare incorporated here by reference.

Though the reaction is rapid, an equilibrium exists between the enamineproduct and the acetoacetoxy/NH reactants. Although the reaction may beconducted at room temperature, the rate of enamine formation increaseswith temperature. Due to the equilibrium, however, an enaminefunctionalized polymer of the invention may have both enamine andacetoacetoxy groups.

Enamine functional polymers or copolymers may also be prepared bypolymerization of enamine functional monomers. An enamine functionalmonomer may be prepared by the reaction of an acetoacetoxy monomer withan amine such as those described above. Polymerization of the resultingenamine functional monomer will produce an enamine functional polymer.This method of enamine polymer preparation is described Mosmer et al.,Polymer Bulletin 32, 419-426 (1994).

The following examples are given to illustrate the invention. It shouldbe understood, however, that the invention is not to be limited to thespecific conditions or details set forth in these examples.

The examples of various coating compositions of the invention use thefollowing materials:

LUPERSOL 575 t-amyl peroxy 2-ethylhexanoate sold by Elf Atochem NorthAmerica.

QP-300 Hydroxyethyl cellulose, sold by Union Carbide Corporation.

AEROSOL OT-75 Anionic Surfactant, sold by Cytec Industries.

TERGITOL NP-40 Nonionic Surfactant, sold by Union Carbide Corporation.

RESIMENE 745 Melamine formaldehyde resin from Cytec Industries.

DESMODUR N 3300 Isocyanate of 6,6-hexane diisocyanate, sold by Bayer,Inc.

BYK 300 Flow aid, sold by Byk Chemie.

MAK Methyl Amyl Ketone, solvent available from Eastman Chemical Company.

FC-430 Fluorosurfactant (98.5% solids), sold by 3M, St. Paul, Minn.

EASTMAN PM Propylene glycol monomethyl ether, sold by Eastman ChemicalCompany.

TAMOL 681 is a dispersant sold by Rohm and Haas Company.

TRITON GR-7M is a surfactant sold by Union Carbide.

DEEFO 495 is a defoamer produced by Ultra Additives Inc.

TI-PURE R-900 is titanium dioxide sold by DuPont.

PROPYLENE GLYCOL is a cosolvent produced at Eastman Chemical Company.

TEXANOL is a cosolvent produced at Eastman Chemical Company.

ASP 072 is a clay-based extender pigment produced by Engelhard.

AMP 95 is a buffer sold by Angus Chemical.

The following methods were used to evaluate the coatings and filmsprepared according to the invention.

Methyl Ethyl Ketone Resistance:

Films cured under the specified conditions were rubbed with a methylethyl ketone (MEK) saturated cloth according to ASTM D5402. Results arereported as the number of double rubs required for breakthrough of thefilm to the substrate.

Gloss:

Gloss was measured on ˜1 mil films coated on Bonderite 1000 pretreatedsteel panels using a Byk-Gardner haze-gloss meter.

Pencil Hardness:

Pencil hardness was measured using a series of pencils containing leadsof differing hardness according to ASTM D3363. The hardness is reportedas the hardest pencil lead that does not penetrate the coating film.

Konig Pendulum Hardness:

The Konig pendulum hardness is determined using a Byk-Gardner pendulumhardness tester according to ASTM D4366. Hardness is reported as thenumber of seconds for the pendulum swing to be damped from a 6° swing toa 3° swing.

Impact Resistance:

Forward and direct impact resistance is determined using a falling dartimpact tester according to ASTM D2794. Results are reported as themaximum in-lbs of force where the film remains intact.

Sodium Hydroxide Stain Test:

A drop of 6 M NaOH solution was placed on the coating and covered with amicroscope cover slide. After 24 hours the panel was washed with waterand the coating inspected for visual damage. A coating with no visualdamage passes the test.

Water Solubility:

Water solubility of a monomer at room temperature was determined byshaking together equal weight amounts of monomer and water and thenisolating the water layer. The water layer was then analyzed for monomercontent using gas chromatography (GC).

Minimum Film Forming Temperature:

Minimum film forming temperature (MFFT) is determined by casting a wetlatex film with a 4-mil applicator cube on an MFFT bar set at atemperature range in which the film will coalesce during drying, pullingthe edge of a brass spatula blade through the film from cold to hot endon the MFFT bar after 30 minutes, and recording the temperature at whichthe blade offers significant resistance to the experimenter.

Hydrolytic Stability:

Hydrolytic stability was measured by means of a potentiometric titrationusing a Brinkman 686 Titrator equipped with a Ross combination glasselectrode was used for the titrations. The basic procedure was to allowthe latex to react with an excess of a strong base of 0.5 N KOH forseveral hours. A sample is taken at given time intervals and titratedagainst a strong acid of 0.5 N HCl to obtain the amount of materialhydrolyzed.

A blank was prepared by taking a 5 mL sample of the latex soon aftertreatment with base and adding 50 mL of deionized (DI) H₂ O. This blankmeasurement was used to determine if any base was immediatelyneutralized upon mixing, i.e. if any free acids were present in themixture initially. The blank value was needed to correct anycalculations based on titration of base during the hydrolysis. Titrationof the blank should only produce one equivalence point resulting fromthe base added. Typical potentials were -25 mV to 25 mV. After thedesired reaction time, another 5 mL sample of the latex and base mixturewas taken and diluted with 50 mL of DI H₂ O and titrated for thepresence of the following two species: the remaining strong base in thesample and the weak base produced by the hydrolysis of the ester. Theexcess strong base gave a first equivalence point while the weak baseformed upon hydrolysis gave a second. Typical potentials were -80 mV forKOH and 200 mV for the hydrolyzed species.

Calculations:

1) Equivalents of hydrolyzable species was calculated based on samplesize of latex to be used, composition of latex and % solids of the latex(as a fraction).

2) For Blank titration to determine any base neutralized by sample uponmixing: ##EQU1## 3) For Hydrolyzed sample titrations to determine amounthydrolyzed: a) based on hydrolyzed weak acid (2^(nd) eq. point):##EQU2## b) based on excess base (1^(st) eq. point): ##EQU3## where EP₁=volume of titrant at first eq. point (mL) from base EP₂ =volume oftitrant at second eq. point (mL) from hydrolyzed material

N=normality of HCl titrant (N) p1 4) For percent hydrolyzed as the mole% of hydrolyzable ester: ##EQU4##

EXAMPLE 1

Synthesis and Purification of 1-acetoxy-2-methoxy-3-butene.

In a 3-liter, 3-necked round bottom flask equipped with a mechanicalstirrer, nitrogen inlet, temperature probe and vigoreux column wasplaced 1200 mL toluene, sodium acetate (88.59 g, 1.08 mol) and2-methoxy-3-buten-1-ol (250.0 g, 2.45 mol). Mixture heated to 60° C.with stirring. Once temperature had stabilized, acetic anhydride (288.83g, 2.80 mol) added dropwise over 2.5 hours. Maintained temperature for1.5 hrs then increased temperature to 70° C. for 1 hour. Gaschromatography showed no trace of starting material in reaction. Begancooling reaction to room temperature. When reaction had cooled to 38°C., one liter of a 5% sodium bicarbonate solution was added at highspeed to decompose any excess acetic anhydride remaining in thereaction. Extracted reaction twice with water, layers separated, theaqueous layer extracted twice with toluene and added to the organiclayer. Organic layer dried with anhydrous magnesium sulfate, filteredand concentrated by rotovap. Yield 222.43 g (63.0%) of a clear,colorless material. ¹ H NMR consistent with 1-acetoxy-2-methoxy butene.

EXAMPLE 2

Synthesis and Purification of 1-acetoacetoxy-2-methoxy-3-butene

In a 500 mL 3-neck round bottom flask was placed 2-methoxy-3-butene-1-ol(164.46 g, 1.61 mol) and t-butyl acetoacetate (430.20 g, 2.50 mol).Reaction flask was equipped with magnetic stir bar, thermocouple,vigreaux column, and a still head with thermometer. Reaction was heatedto 134° C. with stirring for 7 hours, then cooled to room temperature.Product was purified using a short-path distillation apparatus.Distillate was collected until the head temperature exceeded 67° C. NMRof the remaining material indicated the desired product. ¹ H NMR(CDCl₃): d 5.63-5.75 (m, 1H), 5.32-5.40 (m, 2H), 5.06 (s, 1H), 4.10-4.25(m, 2H), 3.82-3.90 (m, 1H), 3.5 (s, 1H), 3.34 (s, 3H), 2.28 (s, 3H),1.96 (s, 3H).

EXAMPLE 3

Copolymerization of 1-acetoxy-2-methoxy-3-butene

In a 500 mL reactor kettle was weighed Eastman PM solvent (180.0 g) andheated to 80° C. Vinyl acetate (216.0 g), 1-acetoxy-2-methoxy-3-butene(54.0 g), and LUPERSOL 575 (5.4 g) weighed into a 500 mL Erlenmeyerflask and pumped into the reactor over three hours. Temperature held at80° C. for one hour after completion of addition, then LUPERSOL 575chaser (0.5 g) was added. Temperature was maintained at 80° C. for anadditional hour before cooling to room temperature. Clear resin producedat 55.43% solids out of a theoretical 60% solids formulation.

EXAMPLE 4

Copolymerization of 1-acetoacetoxy-2-methoxy-3-butene

In a 500 mL two-piece resin reactor was placed 107.7 g propylene glycolmonomethyl ether and heated to 80° C. In a separate container, 80 gvinyl acetate, 40 g of 1-acetoacetoxy-2-methoxy-3-butene, 80 g vinyl2-ethyl hexanoate, and 8.0 g LUPERSOL 575 were mixed: The monomermixture was added to the resin reactor over a 3 hour period. After a onehour hold, 1.0 g of LUPERSOL 575 was added and the reaction held at 80°C. for an additional 1.5 hours. Resin mixture was cooled and poured out.Resin had a solids content of 60.8% and the Tg of the resin was -13° C.

EXAMPLE 5

Coating Made from Copolymer of Example 4

A clear coating formulation was prepared by mixing 29.21 g of the resinin Example 4 above with 6.0 g RESIMENE 745, 1.42 g of a solvent mixtureconsisting of 55% xylene, 32% methyl amyl ketone, 6.5% ethyl ethoxypropionate, 6.5% n-butanol; 0.24 g FC430, and 0.30 g p-toluene sulfonicacid. The components were mixed until homogeneous. The coating mixturewas drawn down on an iron phosphate pretreated steel panel (Bonderite1000) using a wire-wound drawdown bar. The coating was cured at 160° C.for 30 minutes. The resulting coating had 95 MEK double rubs, pencilhardness of 2B, Konig pendulum hardness of 33 seconds, forward impactresistance 160 in-lbs, reverse impact resistance 120 in-lbs.

EXAMPLE 6

Synthesis of Homopolymer

To a 300 mL round bottomed 3-neck flask equipped with a thermocouple,mechanical stirrer, condenser, and a nitrogen inlet was charged 100.00 g3-butene-1,2-diacetate. Contents were heated with stirring to 80° C. 2.0g of LUPERSOL 575 (t-amyl peroxy 2-ethylhexanoate) was added. Thecontents were held for 22 hours at 80° C. then cooled. Conversion ofmonomer to polymer was 65.7%. Number average molecular weight was 8100and the weight-average molecular weight was 13100 by Gel PermeationChromatography.

EXAMPLE 7

Synthesis of Copolymer by Solution Process

107.7 g of propylene glycol monomethyl ether was charged to a 500 mLresin kettle equipped with a mechanical stirrer, nitrogen inlet,thermocouple, and condenser. The solvent was heated to 80° C. withstirring. In a separate vessel, 40 g of 1,2-diacetoxy-3-butene, 100 gvinyl acetate, 60 g vinyl-2-ethylhexanoate, and 8 g LUPERSOL 575 weremixed. The monomer mixture was fed to the heated solvent over a 3 hourperiod. After a one hour hold, 1 g of LUPERSOL 575 was added. Themixture was poured out after 1.5 hours. Measured % solids was 64.73%.Glass transition temperature of the polymer was -6.81° C. as measured asthe midpoint in the inflection of DSC.

EXAMPLE 8

Synthesis of Copolymer by Emulsion Process

A vinyl acetate/3-butene-1,2-diacetate emulsion copolymer was preparedas follows: 248.0 g deionized water, 24.0 g of a 5% solution of QP-300,0.45 g of AEROSOL OT-75, 19.40 g of TERGITOL NP-40, and 1.2 g sodiumcarbonate was charged to a 1-liter two-piece resin kettle equipped witha mechanical stirrer, thermocouple, nitrogen inlet, and condenser. Themixture was heated to 65° C. with rapid stirring. In a separate vessel,320 g vinyl acetate and 80 g of 3-butene-1,2-diacetate were mixed. Whenthe reactor mixture reached 65° C., 40 g of the monomer mixture wasadded. 1.7 g of AEROSOL OT-75 was added to the remaining monomermixture.

Feed #2 was prepared consisting of 1.03 g of 70% aqueous solution oft-butyl hydroperoxide and 29.77 g water. Feed #3 was also preparedconsisting of 0.70 g sodium formaldehyde sulfoxylate dissolved in 30.0 gwater.

After holding for 10 minutes at 65° C., the following were premixed andseparately added to the reactor: (1) 0.25 g of a 1% FeSO₄.7 H₂ O aqueoussolution and 2.0 g water; (2) 0.25 g of a 1% ETDA aqueous solution and2.0 g water; (3) 0.51 g of a 70% aqueous t-butyl hydroperoxide solutionand 4.89 g water; and (4) 0.35 g sodium formaldehyde sulfoxylate and 5.0g water.

After holding for ten minutes at 65° C., the monomer mixture was pumpedin at a rate of 1.7 g/min over 3.5 hours. Thirty minutes after the startof the monomer feed, feeds 2 and 3 were started at a rate of 0.14 g/minover 3.5 hours. Thirty minutes after the completion of feeds 2 and 3,chasers were added consisting of (1) 0.26 g of 70% aqueous t-butylhydroperoxide and 1.94 g water, and (2)0.15 g sodium formaldehydesulfoxylate and 2.0 g water. Thirty minutes later, additional chaserswere added followed by a 30 minute hold at 65° C. The latex was cooled,filtered and packaged.

This latex has a particle size of 305 nm, percent solids of 52.3, pH5.09, viscosity of 602 cP (Brookfield viscosity @ 100 rpm). Minimum filmformation temperature is 17.5° C.

EXAMPLE 9

Synthesis of Emulsion Copolymer Containing 3-butene-1,2-dipropionate

A latex was prepared using the same recipe and procedure as in Example8, except the monomer mixture consisted of 280 g vinyl acetate and 120 gof 3-butene-1,2-dipropionate. Particle size was 301 nm, percent solidswas 52.3, pH 5.13, and viscosity was 1075 cP (Brookfield viscosity @ 100rpm). The minimum film formation temperature was 11.0° C.

EXAMPLE 10

Synthesis of Solution Copolymer of bis(acetoacetate)

To a 500 mL resin kettle equipped with a mechanical stirrer, nitrogeninlet, thermocouple and condenser, 108 g of propylene glycol monomethylether was added. The solvent was heated with stirring to 80° C. In aseparate vessel, 40 g of 1,2-bisacetoacetate-3-butene, 80 g vinylacetate, 80 g vinyl 2-ethyl hexanoate, and 8.0 g of LUPERSOL 575 weremixed. The monomer mixture was added to the heated solvent over a periodof 3 hours. One hour after completion of the addition, 1.0 g of LUPERSOL575 was added. After 1.5 hours the resin was cooled. Mn of the resin was3500 by gel permeation chromatography. The glass transition temperatureof the resin was -9.0° C.

EXAMPLE 11

Crosslinked Coating Using Polymer of Example 10

A clear coating formulation was prepared by mixing 29.16 g of the resinin Example 10 above with 6.0 g RESIMENE 745, 1.47 g of a solvent mixtureconsisting of 55% xylene, 32% methyl amyl ketone, 6.5% ethyl ethoxypropionate, 6.5% n-butanol; 0.27 g FC430, and 0.30 g p-toluene sulfonicacid. The components were mixed until homogeneous. The coating mixturewas drawn down on an iron phosphate pretreated steel panel (Bonderite1000) using a wire-wound drawdown bar. The coating was cured at 160° C.for 30 minutes. The resulting coating had over 200 MEK double rubsindicating substantial curing, pencil hardness of HB, Konig pendulumhardness of 52 seconds.

EXAMPLE 12

Preparation of Copolymer

107.7 g of propylene glycol monomethyl ether (PM) was charged to a 500mL two-piece resin reactor fitted with a condenser, nitrogen inlet, anda mechanical stirrer. The solvent was heated to 80.0° C. In a separatevessel, 40 g of 3-butene-1,2-diol monoacetate, 80 g vinyl acetate, 80 gvinyl propionate, and 8.0 g t-amyl-peroxy-2-ethyl hexanoate (LUPERSOL575) were charged. The monomer mixture was added to the heated solventover a 5 hour period. After a one hour hold, 1 g of LUPERSOL 575 wasadded, and the reaction was held at 80° C. for an additional 1.5 hours.The resin mixture was cooled. The resulting material had a measuredsolids content of 60.1%, viscosity of 380 cps. No unreacted3-butene-1,2-diol monoacetate was detected by gas chromatography. Thenumber average molecular weight was 2600 and the weight averagemolecular weight was 5700 as determined by gel permeation chromatographyusing polystyrene standards.

EXAMPLE 13

Preparation of Copolymer

107.7 g of propylene glycol monomethyl ether (PM) was charged to a 500mL two-piece resin reactor fitted with a condenser, nitrogen inlet, anda mechanical stirrer. The solvent was heated to 80.0° C. In a separatevessel, 30 g of 3-butene-1,2-diol monoacetate, 90 g vinyl acetate, 80 gvinyl 2-ethylhexanoate, and 8.0 g t-amyl-peroxy-2-ethyl hexanoate(LUPERSOL 575) were charged. The monomer mixture was added to the heatedsolvent over a 3 hour period. After a one hour hold, 1 g of LUPERSOL 575was added, and the reaction was held at 80° C. for an additional 1.5hours. The resin mixture was cooled. The resulting material had ameasured solids content of 61.5%, viscosity of 334 cps. No unreacted3-butene-1,2-diol monoacetate was detected by gas chromatography. Thenumber average molecular weight was 3400 and the weight averagemolecular weight was 6400 as determined by gel permeation chromatographyusing polystyrene standards.

EXAMPLE 14

Preparation of Melamine Crosslinked Enamel

An enamel formulation was prepared as follows: To 29.27 g of the resinsolution from Example 13 was added 6.0 g of RESIMENE 745, 1.36 g of asolvent blend (composed of 55% xylene, 32% methyl amyl ketone, 6.5%ethoxy ethyl propionate, and 6.5% n-butanol), 0.29 g of a 25% solutionof FC430 flow control aid in methyl amyl ketone, and 0.30 g of a 30%solution of p-toluene sulfonic acid in isopropanol. The coating wasapplied to iron phosphate pretreated steel test panels and cured in anoven for 30 minutes at 160° C. The final coating thickness was 1.3 mils.The coating had pencil hardness of H, passed 200 MEK double rubs with nomarring, Konig Pendulum hardness of 70 sec. The coating passed a sodiumhydroxide stain test.

EXAMPLE 15

Preparation of Urethane Crosslinked Enamel

Since the polymer of Example 13 is dissolved in a solvent containingactive hydrogen groups, this solvent needed to be replaced beforecrosslinking with an isocyanate functional crosslinker. Solvent wasremoved using a rotary evaporator with a water aspirator vacuum,followed by use of a vacuum pump. The polymer was redissolved in butylacetate at a solids level of 65%.

The urethane coating was prepared as follows: To 18.46 g of the resinsolution above was added 3.00 g DESMODUR N 3300, 0.15 g of BYK 300 flowaid, and 1.51 g of a 1% solution of dibutyl tin dilaurate in MAK. Thecoating was applied to iron phosphate pretreated steel test panels andcured in an oven for 45 minutes at 80° C. The final coating hadthickness of 1.6 mils. Pencil hardness was B, passed 80 MEK double rubs,Konig Pendulum Hardness of 14 sec and had impact resistance of 160in-lbs. The coating passed a sodium hydroxide stain test. The coatinghad a 20° gloss of 87.7 and a 60° gloss of 107.

EXAMPLE 16

Preparation of Enamine

To 5.0 g of the polymer of Example 10 was added 1.2 g of propyleneglycol monomethyl ether, and 0.60 g of butyl amine. The reaction wasstirred at room temperature for 30 minutes. Enamine formation wasmonitored by infrared spectroscopy. A small sample of the reactionmixture was coated onto a zinc selenide crystal and the solvent wasallowed to evaporate. Infrared spectrum indicated an absorbance at 1650cm⁻¹ indicating enamine formation.

EXAMPLE 17

Preparation of Vinyl Acetate and Epoxybutene Ester Based Latexes

Vinyl acetate and epoxybutene (EpB) diester latexes A-H were preparedaccording to the procedure described in Example 8. The composition ofeach latex of A-H is summarized in Table 1 along with theircharacteristics. Latexes A and B represent control polymers for the sakeof comparison. Hydrolytic stability testing was performed using apotentiometric titration on latexes A-F and these results are alsosummarized in Table 1.

CHARACTERIZATION OF LATEX POLYMERS

Percent solids was determined using a CEM Labwave 9000 microwave solidsanalyzer. Viscosity was determined by using a Brookfield DigitalViscometer Model DVII using a #3 LV spindle at 30 rpm. Particle size wasdetermined using a Brookhaven Instruments Corporation BI-90 ParticleSizer. Samples for differential scanning calorimetry (DSC) were preparedby drawing down a sample of latex onto release paper and allowing to airdry for one week. Unreacted monomers were determined using gaschromatography.

                                      TABLE 1                                     __________________________________________________________________________    Vinyl Acetate and Epoxybutene (EpB) Diester Latexes                                         Example                                                                       A   B   C    D    E    F    G    H                              __________________________________________________________________________    Monomer Composition (Wt %)                                                      Vinyl Acetate 80 70 70 80 70 70 80 80                                         Butyl Acrylate 20                                                             VEOVA-10  30                                                                  EpB Dipropionate   30                                                         EpB Dibutyrate    20 30  20                                                   EpB Di(2-ethyl hexanoate)      30  20                                         Trimethoxysilyl methacrylate       0.1 0.1                                    Properties                                                                    Percent solids 49.70 50.11 49.86 50.16 50.33 50.29 49.48 49.27                pH 4.85 5.21 4.73 5.02 4.84 5.09 5.20 5.30                                    Viscosity (cps) 892 392 2344 1504 1920 1172 1504 1248                         Effective Diameter (nm) 333 309 298 332 297 336 324 353                       Mean Diameter (nm) 392 396 346 393 341 386 386 422                            Polydispersity 0.215 0.223 0.192 0.192 0.162 0.190 0.147 0.195                MFFT (° C.) visual 8.6 12.5 10.0 9.9 5.4 3 <0 7.2                      MFFT (° C.) resistance 10.8 17.7 17.1 14.6 13.3 4.5 13.3 13.5                                                        Tg (° C.), DSC                                                        20.7 20.6 21.2 22.2 16.1                                                      11.6 23.6 19.4                   Unreacted monomers                                                            Vinyl Acetate (ppm) 279 82 815 427 1580 1884 31 595                           Comonomer (ppm) ND 54 702 148 2708 0.22% 10 464                               Percent Hydrolyzed                                                            24 Hours 57.8 14.4 99.0 83.6 84.8 17.7                                        72 Hours 80.1 18.0 104.1 96.1 89.9 22.7                                     __________________________________________________________________________

EXAMPLE 18

Preparation of Paint Formulations Based on Vinyl Acetate and EpoxybuteneEster Latexes

Paint formulations were prepared using latexes A-F of Example 17. Apaint formulation based on a commercial vinyl acetate control latex(UCAR 379 available from Union Carbide of Danbury, Conn.) was alsoprepared. These paint formulations are summarized in Table 2. Ingeneral, each paint formulation was prepared by mixing the ingredientslisted in Table 2 for each latex and coalesced using Texanol to aconstant minimum film formation temperature (MFFT) as indicated in Table2. The paint formulation based on the commercial latex was coalesced toa level recommended by the product literature. The grind and thickenermix are described as follows:

Grind

The grind was prepared by weighing and mixing the following ingredients:DI water (75.00 g), Propylene Glycol (150.00 g), TAMOL 681 (21.4 g), AMP95 (6.0 g), and DEEFO 495 (6.0 g). Next, TI PURE-900 (675.0 g) andENGLEHARD ASP 072 (75.0 g) were added under cowles dispersion. Theresulting mixture was allowed to grind until a 7+ Hegman test waspassed.

Thickener Mix

A thickener mix was prepared by mixing the following components: DIwater (50.00 g), Propylene Glycol (10.00 g), and SCT 275 (12.50 g).

TEST METHODS

The paints, coatings and films were evaluated using the followingmethods not described above. All samples were drawn-down and aged underconditions of constant temperature, 72° F., and 50% relative humidity.Paint formulations contained relatively low pigment levels to facilitatecomparisons of relative resin performance.

Paint Viscosity

Paint or Stormer viscosity (in Krebs Units) was measured according toASTM D-856 after 24 hours using a Brookfield KU-1 Krebs-Stormerviscometer.

Gloss

Gloss was measured according to ASTM D-523 on 6 mil (wet) thick filmscast on Leneta 2C opacity paper after 24 hours using micro-Tri-Glossmeter by BYK-Gardner. The appearance of a paint surface was measuredvisually for smoothness and film defects such as bumps and pinholes. An"O.K." rating indicates that no obvious film defects were observed.

Blocking Resistance

Blocking resistance was determined using 6 mil (wet) films on Lenera 2Copacity paper according to ASTM D-4946 Test Method for BlockingResistance of Architectural Paints. Block resistance data was acquiredboth at room temperature and at elevated temperatures for the samples.Films were dried for one day, seven days, and twenty-one days for eachpaint. Block resistance was determined with painted surfacesface-to-face under 1 psi pressure. Room temperature block resistancewere read at one day and seven days face-to-face. The tests werenumerically rated on a scale of 1 to 10. A rating of 10 represented 100%pass where the films came apart with no tack or noise, and 1 represented100% failure where the painted surfaces flowed completely together andcomplete destruction of the films occured upon separation. A rating ofless than 4 indicated some level of destruction of the paint surfaceupon separation.

Wet Block Resistance

Wet block resistance was determined the same as a blocking resistanceexcept that both of the painted surfaces were wiped so that they weredamp and then the wet film surfaces were placed face-to-face under 1 psipressure. Wet block resistance was measured only at room temperature.Films were dried for one day, seven days and twenty-one days for eachpaint. Wet block resistance was read at one day and seven days. Thenumerical test ratings were done the same way as the block resistance.All coatings failed the wet block test.

Print Resistance

Print resistance was determined using 6 mil (wet) films on Leneta 2Copacity paper according to ASTM D-2064 Test Method for Print Resistanceof Architectural Paints using a 4 psi pressure placed on top of a #6rubber stopper which was placed on four layers of cheesecloth after thefilm had dried. Films were dried for one day, seven days and twenty-onedays for each paint. Print resistance was acquired at room temperature.Room temperature print resistance was read after one day and seven dayswith paint surface-to-cheesecloth. The tests were numerically rated on ascale of 1 to 10. A rating of 10 represented a 100% pass with nodemarcation of the film (cloth lifts with no print) and a 1 ratingrepresented 100% fail (the cheesecloth is impressed in the film).

Scrub Resistance

Scrub resistance was determined following ASTM D-2486 Test Method forScrub Resistance of Interior Latex Flat Wall Paints. The coating wasapplied at 7 mil (wet) thickness on Scrub Test Charts Form P121-10N andallowed to dry for seven days. The panel was placed over a shim (1/2inch by 10 mil) on the Gardco Scrub Machine Model D-10V and was wet with5 mL of DI water. Ten grams of Standardized Abrasive Type Scrub Mediumwas placed evenly on the scrub brush and the brush was installed on themachine over the wet panel. The test machine counter was zeroed and thetest was run at the maximum test speed on the machine. After each 400cycles, the brush was removed and 10 grams more of the scrub medium wasapplied evenly on the bristles. The brush was then replaced, 5 mL of DIwater was placed on the panel, and the test was continued. Failure wasdefined as the number of cycles required to remove the paint film fullyin a continuous line across the width of the shim.

Wet Adhesion Test

This procedure tests the coating's adhesion to an aged, alkyd substrateunder wet, scrubbing conditions. A ten mil drawdown of a commercialGloss alkyd paint (green Glidden Industrial Enamel) was made on ScrubTest Charts Form P121-10N. The alkyd film was allowed to age one week atambient conditions, then baked at 110° F. for 24 hours. The panel wasthen aged at least one more week at ambient conditions. Panels treatedin this manner were the test panels for the wet adhesion test. A 7 mil(wet) drawdown of the test paint was made over the aged alkyd panel andthe panel was allowed to air dry for seven days. Constanttemperature/humidity conditions were used during the drying. The testpanel was cross-hatched with a razor and soaked for 30 minutes in waterprior to running the wet adhesion test. The test panel was inspected forblistering and scratched with the fingernail to gauge adhesion. The wetpanel was placed on a Gardco Scrub Machine, Model D-10V. Ten millilitersof a 5% "Lava" soap slurry was added and the nylon scrub brush (WG2000NB) was passed over the scored paint film area. Water was added asneeded to keep the paint film wet. The number of brushing cycles for100% peel was noted.

                                      TABLE 2                                     __________________________________________________________________________    Composition of Formulated Vinyl Acetate-based Paints                          FORMULATION (g)                                                                              UCAR 379                                                                            A   B   C   D   E   F                                    __________________________________________________________________________    Grind          168.07                                                                              168.07                                                                            168.07                                                                            168.07                                                                            168.07                                                                            168.07                                                                            168.07                                 Deionized Water 44.26 44.26 44.26 44.26 44.26 44.26 44.26                     Latex 234.5 234.5 234.5 234.5 234.5 234.5 234.5                               Texanol 6.3 4.66 7.64 5.26 5.88 1.77 1.47                                     DeeFo 495 1 1 1 1 1 1 1                                                       Triton GR-7M 0.25 0.25 0.25 0.25 0.25 0.25 0.25                               Thickener Mix 72.5 72.5 72.5 72.5 72.5 72.5 72.5                              Deionized (DI) Water 8.29 8.29 8.29 8.29 8.29 8.29 8.29                       28% Ammonia 1 1 1 1 1 1 1                                                     Total 536.17 534.53 537.51 535.13 535.75 531.64 531.34                        MFFT latex with coalescent (F) vis  >33.8 >35.2 >32.4 >33.4 >32.7 >33.8       pH of paint 9.5 9.23 9.23 8.95 9.08 9.24 8.6                                  Stormer Viscosity (Kreb Units) 95 89 101 100 93 97 100                      __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Print Resistance (ASTM-D2064) Results                                              1 Day Cure           7 Day Cure           21 Day Cure                    Print                                                                              1 Day Weight                                                                          7 Day Weight                                                                           Print                                                                             1 Day Weight                                                                          7 Day Weight                                                                          Print                                                                              1 Day Weight                                                                          7 Day Weight           Resist. Std     Std   Resist.                                                                              Std     Std  Resist. Std     Std                   Sample Avg Deviation Avg Deviation Sample Avg Deviation Avg Deviation                                                                 Sample Avg                                                                    Deviation Avg                                                                 Deviation           __________________________________________________________________________    UCAR 4.67                                                                             1.15 4.00                                                                             0.00  UCAR                                                                              6.00                                                                             0.00 4.00                                                                             0.00 UCAR 6.00                                                                             0.00 4.00                                                                             0.00                  379     379     379                                                           A 2.00 0.00 2.00 0.00 A 2.00 0.00 2.00 0.00 A 2.67 1.15 2.00 0.00                                                                      B 2.00 0.00                                                                  0.00 0.00 B                                                                   2.00 0.00 2.00                                                                0.00 B 2.00                                                                   0.00 2.00 0.00                                                                 D 2.00 0.00                                                                  2.00 0.00 D                                                                   2.00 0.00 2.00                                                                0.00 D 2.00                                                                   0.00 2.00 0.00                                                                 E 2.00 0.00                                                                  2.00 0.00 E                                                                   2.00 0.00 2.00                                                                0.00 E 2.00                                                                   0.00 2.00 0.00                                                                 C 2.00 0.00                                                                  2.00 0.00 C                                                                   2.00 0.00 2.00                                                                0.00 C 2.00                                                                   0.00 2.00 0.00                                                                 F 0.00 0.00                                                                  0.00 0.00 F                                                                   0.00 0.00 0.00                                                                0.00 F 2.00                                                                   0.00 0.00           __________________________________________________________________________                                                              0.00            

                                      TABLE 4                                     __________________________________________________________________________    Block Resistance (ASTM-D2064) Results                                              1 Day Cure           7 Day Cure           21 Day Cure                    Block                                                                              1 Day Weight                                                                          7 Day Weight                                                                           Block                                                                             1 Day Weight                                                                          7 Day Weight                                                                          Block                                                                              1 Day Weight                                                                          7 Day Weight           Resist. Std     Std   Resist.                                                                              Std     Std  Resist. Std     Std                   Sample Avg Deviation Avg Deviation Sample Avg Deviation Avg Deviation                                                                 Sample Avg                                                                    Deviation Avg                                                                 Deviation           __________________________________________________________________________    UCAR 0.00                                                                             0.00 0.00                                                                             0.00  UCAR                                                                              2.00                                                                             1.00 1.33                                                                             0.58 UCAR 3.00                                                                             0.00 3.00                                                                             0.00                  379     379     379                                                           A 0.33 0.58 0.33 0.58 A 0.33 0.58 0.00 0.00 A 2.33 0.58 0.67 0.58                                                                      B 0.00 0.00                                                                  0.00 0.00 B                                                                   0.00 0.00 0.00                                                                0.00 B 0.00                                                                   0.00 1.00 0.00                                                                 D 0.00 0.00                                                                  0.00 0.00 D                                                                   0.33 0.58 0.00                                                                0.00 D 2.00                                                                   0.00 0.67 0.58                                                                 E 0.67 0.58                                                                  0.00 0.00 E                                                                   0.67 0.58 0.67                                                                0.58 E 2.00                                                                   0.00 0.67 0.58                                                                 C 2.67 0.58                                                                  2.67 0.58 C                                                                   1.00 0.00 1.33                                                                0.58 C 2.67                                                                   0.58 3.00 0.00                                                                 F 0.3 0.58                                                                   0.00 0.00 F                                                                   0.00 0.00 0.00                                                                0.00 F 0.00                                                                   0.00 0.33           __________________________________________________________________________                                                              0.58            

                  TABLE 5                                                         ______________________________________                                        Scrub Resistance (ASTM-D2486) Results                                               1 WEEK 40° F./                                                                      3 WEEK 40° F./                                                                      6 WEEK 40° F./                           50% SCRUB 50% SCRUB 50% SCRUB                                                             Std.           Std.         Std.                                  Sample Average Deviation Average Deviation Average Deviation                ______________________________________                                        UCAR  2360    450      2332  507    2875  251                                   379                                                                           A 1269 123 579  17 1071 159                                                   B 1235 103 722  46  916  96                                                   D  301  13 267  20  311  24                                                   E  304  26 156  12  291  14                                                   C <200 <200  <200  <200   75  10                                              F  694  45 715  93 1301  91                                                 ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Wet Adhesion Results                                                            100% LOSS WET ADHESION                                                               3 Day Data      1 Week Data                                          Sample   Average Std. Deviation                                                                            Average                                                                             Std. Deviation                             ______________________________________                                        UCAR 379 64      24          37    10                                           A 10  6 12  2                                                                 B 25 20 62 20                                                                 D 352  111  51 13                                                             E 17 14 78 14                                                                 C 10 13 26  8                                                                 F  7  5 18  7                                                               ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Gloss Results                                                                   GLOSS                                                                         SAM-    20      Std.   60    Std.   85    Std.                                PLE degree Deviation degree Deviation degree Deviation                      ______________________________________                                        UCAR                                                                            #1 30.86 1.318 71.4 1.048 85.24 1.156                                         #2 31.2 0.954 71.62 0.974 83.9 0.641                                          #3 30.4 0.878 71.34 0.9 84.48 1.274                                           A                                                                             #1 12.44 0.205 6.32 0.263 81 0.544                                            #2 11.86 0.646 54.92 1.249 82.32 0.636                                        #3 11.98 0.682 55.14 1.363 81.94 1.406                                        B                                                                             #1 21.88 0.587 64.04 0.68 82.46 1.573                                         #2 20.5 1.476 62.2 2.464 80.96 2.803                                          #3 22.74 1.357 64.36 1.998 82.66 1.369                                        D                                                                             #1 6.04 0.205 42.8 1.12 81.92 1.075                                           #2 5.82 0.231 42.78 0.926 81.16 0.958                                         #3 6.48 0.24 45.42 1.33 81 0.88                                               E                                                                             #1 6.46 0.079 45.46 0.101 78.32 0.711                                         #2 6.6 0.063 45.68 0.495 78.96 1.076                                          #3 7.04 0.135 46.06 0.634 78.4 1.357                                          C                                                                             #1 5.14 0.079 41.62 0.519 82.12 0.835                                         #2 5.26 0.101 42.16 0.516 80.14 0.708                                         #3 5.64 0.135 43.62 0.658 80.98 0.421                                         F                                                                             #1 41.46 1.199 73.88 0.159 85.22 1.295                                        #2 40.72 1.101 73.64 0.28 86.36 0.939                                         #3 40.56 1.149 74.12 0.511 85.76 1.372                                      ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Gloss Appearance Results                                                        Sample    Appearance (Gloss Panels)                                         ______________________________________                                        UCAR 379                                                                              O.K.         O.K.       O.K.                                            A O.K. O.K. O.K.                                                              B Pinholes Pinholes Pinholes                                                  D O.K. O.K. O.K.                                                              E O.K. O.K. O.K.                                                              C O.K. O.K. O.K.                                                              F O.K., O.K., O.K.,                                                            but Very Tacky but Very Tacky but Very Tacky                               ______________________________________                                    

The claimed invention is:
 1. A polymer comprising the free-radicalpolymerization product of:a monomer of formula (I): ##STR7## where R1and R2 are both a --C(O)R3 group; R3, which can be the same ordifferent, is selected from the group consisting of a C₁ -C₂₄ alkylgroup, an aromatic or heteroaromatic group, a C₃ -C₈ cycloalkyl or C₂-C₇ heterocyclic group, and a --CH₂ --C(O)--R4 group; R4 is a C₁ -C₆alkyl group;and an ethylenically unsaturated monomer.
 2. A polymer ofclaim 1, wherein the ethylenically unsaturated monomer is at least oneselected from the group consisting of an allylic compound, a vinyliccompound, a styrenic compound, an α,β-unsaturated compound, an acryliccompound, and an alkene.
 3. A polymer of claim 2, wherein R3 is anethyl, propyl, or 3-heptyl group; and said ethylenically unsaturatedmonomer is vinyl acetate.
 4. A coating composition comprising thepolymer of claim 1, water, a solvent, a pigment and, optionally, anadditive or a filler.
 5. A coating composition of claim 4, wherein R3 isan ethyl, propyl, or 3-heptyl group; andsaid ethylenically unsaturatedmonomer is vinyl acetate.
 6. A coating composition of claim 5, whereinR3 is the same for R1 and R2.
 7. A coating composition of claim 4,wherein said coating composition is a paint, an architectural coating, amaintenance coating, an industrial coating, an automotive coating, atextile coating, an ink, an adhesive, or a coating for paper, wood, orplastic.
 8. A coated article comprising a substrate coated with acoating composition of claim
 4. 9. A coated article of claim 8, whereinsaid substrate is selected from the group consisting of paper, plastic,steel, aluminum, wood, gypsum board, and primed or unprimed galvanizedsheeting.
 10. A method of making a vinyl polymer comprising the stepof:polymerizing under free-radical conditions:a monomer of formula (I):##STR8## where R1 and R2 are both a --C(O)R3 group; R3, which can be thesame or different, is selected from the group consisting of a C₁ -C₂₄alkyl group, an aromatic or heteroaromatic group, a C₃ -C₈ cycloalkyl orC₂ -C₇ heterocyclic group, and a --CH₂ --C(O)--R4 group; R4 is a C₁ -C₆alkyl group;and an ethylenically unsaturated monomer.
 11. The method ofclaim 10, wherein the free-radical polymerization step is a semi-batchsolution, or emulsion free-radical polymerization step.
 12. The methodof claim 10, wherein the ethylenically unsaturated monomer is at leastone selected from the group consisting of an allylic compound, a vinyliccompound, a styrenic compound, an α,β-unsaturated compound, an acryliccompound and an alkene.